The commercialization of V-based catalysts for the selective catalytic reduction of NOx by NH
3 (NH
3-SCR) is hindered by their narrow operating temperature window, insufficient low-temperature (LT) activity, and severe SO
2-to-SO
3 oxidation. To bridge this gap, we herein
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The commercialization of V-based catalysts for the selective catalytic reduction of NOx by NH
3 (NH
3-SCR) is hindered by their narrow operating temperature window, insufficient low-temperature (LT) activity, and severe SO
2-to-SO
3 oxidation. To bridge this gap, we herein introduced Nb and hexagonal BN into a VW/TiO
2 system to simultaneously enhance its LT SCR activity, suppress undesired side reactions, and improve durability. Nb incorporation promoted V
5+/V
4+ redox cycling and enhanced lattice oxygen mobility, thus reducing the apparent activation energy and suppressing SO
2 oxidation at elevated temperatures. However, excessive Nb loading induced NH
3 oxidation and N
2O formation. This drawback was mitigated by introducing BN as a dispersion promoter, which helped secure high catalytic performance at a reduced Nb content. The VWNb/Ti-BN catalyst achieved superior NOx conversion and N
2 selectivity over a wide temperature range and benefited from notably suppressed NH
3 oxidation and SO
2-to-SO
3 oxidation. Kinetic analysis revealed that Nb primarily lowered the reaction energy barrier via redox property enhancement, whereas BN accelerated surface reaction turnover by stabilizing and dispersing active acidic sites, markedly increasing the turnover frequency without reducing the activation energy. In situ spectroscopic analysis confirmed the accelerated consumption of adsorbed NH
3 species and enhanced formation of reactive NOx intermediates, indicating SCR pathway enhancement. After aging in the presence of SO
2 and H
2O, the best-performing honeycomb-type monolithic catalyst retained and NOx conversion of >80%, demonstrating excellent long-term durability under practical conditions. A composition-aware machine learning model based on log-ratio-transformed variables quantitatively identified the synergistic balance among V, Nb, W, BN, and TiO
2 as the dominant factor governing LT SCR performance. Thus, this work provides valuable mechanistic insights and a strategy for designing wide-temperature-window SCR catalysts with improved activity, selectivity, and resistance to sulfur poisoning.
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